Glass-ceramic containing nanoscale barium titanate and process for the production thereof

ABSTRACT

A process for the production of a glass-ceramic comprises the following steps:
         a) providing a mixture comprising at least SiO 2 , Al 2 O 3 , BaO and TiO 2 ,   b) melting the mixture in order to produce a glass phase,   c) cooling the glass phase, and   d) ceramicizing the glass phase. In the process, the glass phase is heated over the course of at most 5 minutes, preferably over the course of at most 3 minutes, to a temperature in the region of the crystallization temperature of Ba 1-x Z 1   x Ti 1-y Z 2   y O 3 , whereby Z 1  is an element selected from the group consisting of Sr, Ca, Ce, Pb, La and Sm, whereby Z 2  is an element selected from the group consisting of Zr, Hf, Nb, V, Y, Sc and Ta, and whereby x and y are each independently of one another 0≦x,y≦0.5, preferably 0≦x,y≦0.1, but substantially below the crystallization temperature of Ba[Al 2 Si 2 O 8 ].

CROSSREFERENCES TO RELATED APPLICATIONS

This application claims priority from German patent application 10 2009 024 645.2, filed on Jun. 4, 2009. The entire content of this priority application is incorporated herein by reference.

BACKGROUND OF THE INVENTION

The present invention relates to a glass-ceramic, a process for the production of a glass-ceramic as well as electronic components comprising a dielectric.

There is currently an increasing need for energy storage for times ranging from microseconds to days and a large amount of electrical energy. If the energy stores used in this context are to be quick to charge or discharge, electrical capacitors are often used for this purpose. Capacitors of this type require materials having special dielectric properties. Of particular interest in this context are a high breakdown voltage and, in order to obtain a high storage density, also a high dielectric constant, preferably in combination with a flat temperature profile, in order to make it possible to use the capacitor in a broad temperature range.

In the prior art, polypropylene films are generally used as the dielectric, particularly for high performance capacitors. However, the dielectric breakdown voltage of about 1 V/cm for a dielectric of this type limits the density with which energy can be stored.

In order to increase the storage density electrolytic capacitors, for example, have been proposed. Jeol in Japan has announced a dual-layer electrolytic capacitor having a storage density in the order of magnitude of 20 Wh/l (JP 11288852 A2). However, the electrolytes used as the dielectric in capacitors of this type are generally chemically reactive, and harmful to the environment and, in some cases, can even be explosive.

It is further known to use glasses as the dielectric, e.g. for capacitors. Capacitors which use glass as the dielectric are, however, often complicated to produce and accordingly expensive.

It is furthermore known to use ceramic materials, in particular also Ba—TiO₃ ceramics, as the dielectric. In this case, however, the dielectric breakdown voltage of ceramics is limited by their residual porosity.

SUMMARY OF THE INVENTION

It is therefore an object of the present invention to specify a material having improved dielectric properties, in particular a high breakdown voltage and a high dielectric constant, preferably in combination with a flat temperature profile, as well as a process for the production of said material and electrical components using said material.

According to the invention, the object is achieved by a glass-ceramic comprising, as main crystalline phase, a perovskite phase of the following formula: Ba_(1-x)Z¹ _(x)Ti_(1-y)Z² _(y)O₃, in which Z¹ is an element selected from the group consisting of Sr, Ca, Ce, Pb, La and Sm, in which Z² is an element selected from the group consisting of Zr, Hf, Nb, V, Y, Sc and Ta, and in which x and y are each independently of one another 0≦x,y≦0.5, preferably 0≦x,y≦0.1, whereby size of the crystallites is in the range of 10 nm to 50 μm, preferably of 100 nm to 1 μm.

The object is further achieved by a process for the production of a glass-ceramic, comprising the following steps:

-   -   a) providing a mixture comprising at least SiO₂, Al₂O₃, BaO and         TiO₂,     -   b) melting the mixture in order to produce a glass phase,     -   c) cooling the glass phase, and     -   d) ceramicizing the glass phase, whereby the glass phase is         heated over the course of at most 5 minutes, preferably over the         course of at most 3 minutes, to a temperature in the region of         the crystallization temperature of Ba_(1-x)Z¹ _(x)Ti_(1-y)Z²         _(y)O₃, whereby Z¹ is an element selected from the group         consisting of Sr, Ca, Ce, Pb, La and Sm, whereby Z² is an         element selected from the group consisting of Zr, Hf, Nb, V, Y,         Sc and Ta, and whereby x and y are each independently of one         another 0≦x,y≦0.5, preferably 0≦x,y≦0.1, but substantially below         the crystallization temperature of Ba[Al₂Si₂O₈].

The object is further achieved by an electronic component comprising a dielectric, whereby the dielectric contains a glass-ceramic according to the invention. This component is preferably a component selected from the group consisting of the capacitors, the frequency filters and the antennas and is, in particular, a high-performance capacitor.

Within the context of the invention, a glass-ceramic is understood to be a material obtained via a homogeneous melt. This melt is super cooled into a glass-like state in order to form a glass, and, in a second step independent of the first heating step, the glass is treated with a precisely defined temperature profile over time, in order to enable the controlled growth of crystals in the glass.

In this context, the crystallization temperatures of Ba_(1-x)Z¹ _(x)Ti_(1-y)Z² _(y)O₃ and Ba[Al₂Si₂O₈] can be determined using standard processes known to a person skilled in the art such as differential thermoanalysis (DTA) or temperature-dependent X-ray diffraction.

It has been found that the process according to the invention can be used to produce glass-ceramics, in which Ba_(1-x)Z¹ _(x)Ti_(1-y)Z² _(y)O₃ crystallites having a size in the nanometre range are incorporated in a continuous glass phase in a dense and pore-free manner. The lack of pores means that the glass-ceramic of the invention has an increased breakdown voltage, e.g. compared to porous ceramics. In addition, the size of these crystallites means that virtually every individual Ba_(1-x)Z¹ _(x)Ti_(1-y)Z² _(y)O₃ crystallite forms an individual ferroelectric domain which can reorient itself in an external electric field through very small thermal fluctuations. This results in very high dielectric constants and is also referred to as a superparaelectric effect. In addition, the temperature dependence of the dielectric constant is also relatively flat, since the presence of small crystallites having diameters in the region of the ferroelectric domains blurs the otherwise sharp electric transitions when the crystal structure changes as a result of temperature.

Furthermore, the present process also makes it possible to reduce, if not even completely prevent, the formation of other, undesirable crystallites, such crystallites of Ba[Al₂Si₂O₈], also referred to as Ba-celsian, or of BaTi₂Si₂O₈, also referred to as fresnoite.

The glass-ceramics which can be produced, for example, according to the above-mentioned process and have been found by the present inventors thus form materials which are outstandingly suitable for use in electrical components and, in particular on account of the high dielectric constant, can be used with preference in capacitors and, in particular, in high-performance capacitors.

In the present process, the glass produced in steps b) and c) is heated over the course of a very short time, in particular over the course of at most 5 minutes and preferably over the course of at most 3 minutes, to a temperature in the region of the crystallization temperature of Ba_(1-x)Z¹ _(x)Ti_(1-y)Z² _(y)O₃, which usually lies in the range of about 800 to 880° C. In this context, the glass does not necessarily have to be heated completely to the crystallization temperature in the process. The crystallization of Ba_(1-x)Z¹ _(x)Ti_(1-y)Z² _(y)O₃ already begins to set in at a temperature below the actual crystallization temperature, this involving an exothermic process, such that the heat still required to reach the crystallization temperature can be produced by the crystallization of the Ba_(1-x)Z¹ _(x)Ti_(1-y)Z² _(y)O₃.

Here, it is particularly preferable to avoid heating the glass completely to the crystallization temperature of Ba_(1-x)Z¹ _(x)Ti_(1-y)Z² _(y)O₃, in order to prevent the temperature of the glass from overshooting the crystallization temperatures of undesirable crystallites, which may result from the evolution of heat during the crystallization of Ba_(1-x)Z¹ _(x)Ti_(1-y)Z² _(y)O₃.

In this case, it should also be noted that although it is preferable, in the process of the invention, for the glass to remain below the crystallization temperature of Ba[Al₂Si₂O₈] at all times, it is also possible for this temperature to be exceeded locally limited within the glass or briefly, in so far as this does not result in an excessive crystallization of Ba[Al₂Si₂O₈].

In one embodiment of the process, the mixture in step a) comprises at least the following:

10-20 mol % SiO₂,

0-10 mol % Al₂O₃,

30-45 mol % BaO,

30-40 mol % TiO₂.

It has been found that the use of a mixture of the above-mentioned oxides in the above-mentioned quantitative ratios can produce glass-ceramics having a particularly high dielectric constant and a particularly advantageous temperature profile.

In a further embodiment of the invention, the mixture in step a), or the glass-ceramic, further comprises at least one oxide selected from the group consisting of Sb₂O₃, As₂O₃ and Bi₂O₃.

It has been found that the addition of the above-mentioned oxides makes it possible to enlarge the difference in the crystallization temperatures between Ba_(1-x)Z¹ _(x)Ti_(1-y)Z² _(y)O₃ and Ba[Al₂Si₂O₈], and therefore it becomes easier to specifically crystallize out the Ba_(1-x)Z¹ _(x)Ti_(1-y)Z² _(y)O₃ desired according to the invention as opposed to the Ba[Al₂Si₂O₈], making it easier to carry out the process and resulting in a higher-quality glass-ceramic.

In one embodiment of the above-mentioned measure, the mixture in step a), or the glass-ceramic, comprises 0.01 to 3 mol %, preferably 0.1 to 1 mol %, and particularly preferably 0.1 to 0.5 mol % of the at least one oxide selected from the group consisting of Sb₂O₃, As₂O₃ and Bi₂O₃.

It has been found that the addition of the above-mentioned quantities of Sb₂O₃, As₂O₃ or Bi₂O₃ makes it possible to effectively enlarge the temperature difference between the crystallization temperature of the desired Ba_(1-x)Z¹ _(x)Ti_(1-y)Z² _(y)O₃ and the crystallization temperature of the undesired Ba[Al₂Si₂O₈], without negatively effecting the quality of the resulting glass-ceramic and without having to use excessive quantities of possibly harmful oxides.

In a further embodiment of the invention, the mixture in step a), or the glass-ceramic, further comprises at least one oxide selected from the group consisting of P₂O₅ and B₂O₃.

The addition of P₂O₅ or B₂O₃ is advantageous since these act as glass-forming agents and thus promote the formation of a homogeneous glass phase.

In a further embodiment of the process of the invention, the mixture in step a) further comprises at least one oxide of an element selected from the group consisting of Sr, Ca, Ce, Pb, La, Sm, Zr, Hf, Nb, V, Y, Sc and Ta.

It has been found that the addition of oxides of the above-mentioned elements makes it possible to influence the electrical properties of the glass-ceramics produced according to the process of the invention, in order to match the latter even better to the desired end use.

In a further embodiment of the process of the invention, the ceramicization in step d) takes place using an IR radiator and, in particular, under PID control with the aid of a pyrometer.

It has been found that the rapid heating of the glass phase in step d) of the process according to the invention can be achieved particularly effectively using an IR radiator, whereby an especially precise temperature control is made possible by using PID control with the aid of a pyrometer.

In a further embodiment of the invention, the glass phase, during the ceramicization in step d), after heating is held for a period of 1 minute to 1 hour at a temperature in the region of the crystallization temperature of Ba_(x)Z¹ _(1-x)Ti_(y)Z² _(1-y)O₃.

It has been found that the crystal growth in the glass phase is influenced positively and particularly high-quality glass-ceramics are obtained by holding the temperature in the region of the crystallization temperature for 1 minute to 1 hour.

In a further embodiment of the glass-ceramic of the invention, the volumetric content η of the perovskite phase is 0.3≦η≦0.95.

It has been found that a glass-ceramic having particularly good electrical but also mechanical properties can be obtained if the Ba_(1-x)Z¹ _(x)Ti_(1-y)Z² _(y)O₃ perovskite phase is present in the above-mentioned quantities.

In a further embodiment, the glass-ceramic of the invention has a dielectric constant of ∈′>4000, preferably of ∈′>6000 and particularly preferably of ∈′>8000.

In a further embodiment, the glass-ceramic of the invention has a dielectric loss angle at 10 kHz of tan δ<5·10⁻², preferably of tan δ<2·10⁻².

In a further embodiment, the glass-ceramic of the invention has a dielectric strength given a thickness of 100 μm of >20 kV/mm, preferably of >100 kV/mm.

Glass-ceramics having the above-mentioned properties are particularly well-suited for use in high-performance capacitors.

It goes without saying that the features of the invention mentioned above, and those still to be explained below, can be used not only in the combination given in each case but also in other combinations or on their own, without departing from the scope of the present invention.

BRIEF DESCRIPTION OF THE DRAWINGS

Further features and advantages of the invention are apparent from the following description of preferred exemplary embodiments, with reference to the drawings, in which:

FIG. 1 is a schematic view of a capacitor;

FIG. 2 a) to c) show differential thermoanalysis (DTA) graphs for the glasses produced according to Examples 1 to 3;

FIG. 3 is a plan view of an SWIR heating unit used for ceramicization;

FIG. 4 shows a schematic cross section through the SWIR heating of FIG. 3;

FIG. 5 shows a graph representing the heating profile for ceramicizing the glass phases of Examples 4 to 6;

FIG. 6 shows a scanning electron microscope (SEM) image of the glass-ceramic of Example 4;

FIG. 7 shows an X-ray diffraction (XRD) analysis of the glass-ceramic of Example 4;

FIG. 8 shows a graph in which the dielectric constant of the glass-ceramic of Example 4 is plotted against frequency at room temperature; and

FIG. 9 a) and b) show graphs in which the dielectric constant is plotted against temperature for the glass-ceramic of Example 4 and a BaTiO₃ single crystal respectively.

DESCRIPTION OF PREFERRED EMBODIMENTS

In FIG. 1, a ceramic capacitor is denoted in its entirety by reference numeral 10. In a capacitor 10 of this type, there is a respective alternating arrangement of a dielectric in the form of glass-ceramic plates, one of these being denoted here by way of example with reference numeral 12, and electrodes in the form of metal foils, one of which is denoted here by way of example with reference numeral 14. The metal foils 14 each project in alternating fashion beyond one of the two sides of the stack of glass-ceramic plates 12, where they are electrically connected to one another via electrical contacts 16, 16′. Electrical connections 17 and 17′, by means of which the capacitor 10 can for example be connected to a printed circuit board, are then correspondingly arranged in each case at the contacts 16 and 16′. Owing to its structure, a capacitor 10 of this type is also referred to as a layered capacitor. The assembly comprising glass-ceramic plates 12 and metal foils 14 is preferably additionally surrounded by a housing 18, which is shown here merely by dashed lines and can be formed, for example, by pouring the stack into a synthetic resin.

EXAMPLES Examples 1 to 3

In order to demonstrate the effect of the addition of Sb₂O₃, three example glasses which respectively contained 0, 0.15 and 0.20 mol % Sb₂O₃ as additive were produced from the starting materials listed in Table 1 below. For this purpose, the respective starting materials were mixed in a platinum crucible, and a glass was melted and homogenized therefrom at a temperature of 1450° to 1600° C. A homogeneous, clear, transparent glass was obtained after cooling to room temperature. The glasses obtained in this way were then subjected to differential thermoanalysis using a Netzsch STA 409PC differential thermoanalyser. The resulting curves are shown in FIGS. 2 a to 2 c. There are two main peaks in all three curves obtained, with the first peak, which occurs at 847, 827 and 818° C. respectively, being the peak for the crystallization of the BaTiO₃. The second peak, which occurs at 890, 958 and 961° C. respectively, is the peak for the crystallization of Ba[Al₂Si₂O₈] (hereafter Ba-celsian). It becomes clear from these curves that there is a difference of only about 43 K between the crystallization temperatures without the addition of Sb₂O₃. However, this difference is increased to about 131 K if just 0.15 mol % Sb₂O₃ are added, and, if 0.2 mol % Sb₂O₃ are added, this difference is about 143 K.

On account of this increased temperature difference between the two crystallization temperatures, the addition of Sb₂O₃ makes it significantly easier to selectively crystallize out BaTiO₃ as opposed to Ba-celsian and to thus obtain glass-ceramics having the desired high dielectric constant.

TABLE 1 Example number 1 2 3 mol % % by wt. mol % % by wt. mol % % by wt. SiO₂ 18.15 10.22 16.18 8.93 16.17 8.92 Al₂O₃ 5.35 5.11 7.09 6.65 7.09 6.64 B₂O₃ 1.75 1.14 0.00 0.00 0.00 0.00 BaO 40.00 57.49 37.84 53.33 37.82 53.25 TiO₂ 34.75 26.03 37.74 27.71 37.72 27.67 Sb₂O₃ 0.00 0.00 0.15 0.39 0.20 0.53 La₂O₃ 0.00 0.00 1.00 2.99 1.00 2.99 Sum 100.00 100.00 100.00 100.00 100.00 100.00 total

Examples 4 to 6

In a further experiment, three glass-ceramics were produced using the mixtures shown in Table 2 below.

TABLE 2 Example number 4 5 6 mol % % by wt. mol % % by wt. mol % % by wt. SiO₂ 18.10 10.21 18.10 10.20 18.10 10.34 Al₂O₃ 7.10 6.80 7.10 6.79 7.10 6.88 B₂O₃ 0 0 0 0 3.00 1.99 BaO 39.00 56.14 39.00 56.08 37.50 54.67 TiO₂ 35.80 26.85 35.80 26.83 34.26 26.03 Sb₂O₃ 0 0 0.04 0.10 0.04 0.10 Sum 100.00 100.00 100.00 100.00 100.00 100.01 total

Preparation

In a platinum crucible a glass was melted from the respective starting materials (cf. Table 2) at a temperature of about 1450 to 1600° C. and homogenized. A homogeneous, clear, transparent glass was obtained after cooling to room temperature. Samples which were to be ceramicized in the form of plates having a diameter of 60 mm and a thickness of 0.5 mm were separated from said glass. Glass samples of this type were placed into an IR surface heating unit (see Table 3 for technical data), as shown schematically in FIGS. 3 and 4. The SWIR surface heating unit (shortwave infrared heating unit), denoted in FIGS. 3 and 4 in its entirety by reference numeral 20, is heated using shortwave infrared radiant heaters 26 as per Table 3. The radiators 26 are arranged under the ceiling area parallel to the width of the unit. A suitable support 22 made from a high-temperature-stable material which is highly absorptive or highly diffractive for IR radiation is arranged at the base of the SWIR surface heating unit 20. By way of example, this may be Al₂O₃, quartz glass or Quarzal, preferably in powder form. The samples 24 of the starting glass which are to be ceramicized are placed on the support 22.

The glasses were then subjected to ceramicization according to the temperature profile shown in FIG. 5. The ceramicization was carried out under PID control with the aid of a pyrometer 28, which measures the surface temperature of the sample. It was thereby possible to keep the actual temperature of the sample in wide ranges in the region of the desired temperature. The actual-temperature peak occurring shortly after 300 s is caused by the thermal energy released by the beginning crystallization of the BaTiO₃. In order to counteract excessive heating of the sample and thus prevent excessive crystallization of Ba-celsian, at this point in time the control had switched off the IR radiation completely, until the surface temperature of the sample returned to the desired value again. When latent heat is no longer released from the crystallization, the heating unit switches back on automatically in order to reach the desired temperature. After complete ceramicization (about 1 minute), the sample is rapidly cooled to a temperature below 800° C. (650° C.-800° C.) and then cooled to room temperature at a rate of about 10 K/min. The latter serves to obtain materials which are as free from mechanical stresses as possible.

TABLE 3 Unit: SWIR surface heating unit Dimensions (w × d × h): 450 mm × 370 mm × 345 mm (internal dimensions from wall to wall) Material of walls: Quarzal all-round, wall thickness 30 mm Thermal insulation: None Radiator type: Twin tube radiator 33 × 15 mm² Radiator arrangement: Under the ceiling area, parallel to the width of the unit Number of radiators: 9 Helix per radiator: 2 Power per helix: 8.4 kW Colour temperature: 3000 K

FIG. 6 shows a scanning electron microscope image (SEM image) of the glass-ceramic obtained according to Example 4. For the SEM measurement, the sample was ground on the surface and a layer of carbon approximately 10 nm thick was vapour-deposited thereon. The sample was then investigated using a Zeiss Gemini 1530 scanning electron microscope. In this illustration, the individual crystallites are shown as light areas firmly embedded in the darker glass phase. The volumetric content of the perovskite phase is about 70% (η≈0.7).

It is clear from this illustration that the BaTiO₃ crystallizes as needle-shaped crystals having lengths of about 200 nm and a diameter of about 50 nm. Here, the diameter of the BaTiO₃ crystals is in an order of magnitude corresponding substantially to an individual ferroelectric domain, and therefore these can easily orient themselves in an external electric field purely by thermal fluctuations. This results in the desired high dielectric constant and is also often referred to as a super-paraelectric effect.

FIG. 7 shows an X-ray diffraction analysis of the glass-ceramic from Example 4. The spectrum obtained is shown here as a curve, while the theoretical peaks for BaTiO₃ are shown beneath the curve. The X-ray spectrum of the sample was recorded using a Panalytical X′ pert Pro X-ray diffractometer. The comparison of the spectrum obtained with the theoretical spectrum of BaTiO₃ shows that BaTiO₃ forms the dominant crystal phase in the sample, as desired.

In FIG. 8, the dielectric constant (∈′) of the glass-ceramic from Example 4 is plotted against frequency. It is clear from this graph that values greater than 10 000 can be achieved for the dielectric constant depending on the frequency, and that the course of the dielectric constant is also relatively flat. The relatively severe drop of the curve in the region of 1 kHz is thereby not a property of the material, but only an artefact caused by the measurement apparatus. In order to measure the dielectric constant, small sheets of the glass-ceramic from Example 4 having a diameter of 20-40 mm and a thickness of about 0.5 mm were contacted on both sides with conductive silver paint. An impedance analyser (alpha Analyzer from Novocontrol) was used to determine the capacitance and the dielectric loss as a function of frequency. At high frequencies, the impedance |Z|˜1/(ωC) with the angular frequency ω and the capacitance C is so low that very high currents occur. This results in the apparent drop in ∈′ at high frequencies.

In FIG. 9 a, the dielectric constant of the glass-ceramic from Example 4 is plotted as a function of temperature. In order to measure these properties, the sample was placed in a cryostat with temperature control, and the impedance was measured as described above. It can be seen from this curve that the dielectric constant in a temperature range of −55 to 150° C. displays a very flat temperature response and deviates only by values of ±15% from the median. The glass-ceramic of Example 4 thus complies with the electronic standard for capacitor materials X8R.

For comparison, in FIG. 9 b the course of the dielectric constant is plotted against temperature for a single crystal of pure BaTiO₃ (source: B. Jaffe, W. R. Cook, H. Jaffe; Piezoelectric ceramics, Academic Press, London, 1971, p. 53). In contrast to the glass-ceramic comprising nanocrystalline BaTiO₃, the single crystal displays a considerably less flat temperature profile of the dielectric constant owing to the changes in the crystal lattice which occur at different temperatures, with sharp peaks occurring in the dielectric constant, which are undesirable in electronic circuits exposed to different temperatures, particularly at the transition from the rhombohedral structure to the orthorhombic structure in the region of −100° C. and at the transition from the orthorhombic structure to the tetragonal structure at about 0° C. 

1. A method for producing a glass-ceramic, comprising the following steps: a) providing a mixture comprising at least SiO₂, Al₂O₃, BaO and TiO₂, b) melting said mixture in order to produce a glass phase, c) cooling said glass phase, and d) ceramicizing said glass, whereby said glass phase is heated over the course of at most 5 minutes, preferably over the course of at most 3 minutes, to a temperature in the region of the crystallization temperature of Ba_(1-x)Z¹ _(x)Ti_(1-y)Z² _(y)O₃, whereby Z¹ is an element selected from the group consisting of Sr, Ca, Ce, Pb, La and Sm, whereby Z² is an element selected from the group consisting of Zr, Hf, Nb, V, Y, Sc and Ta, and whereby x and y are each independently of one another 0≦x,y≦0.5, preferably 0≦x,y≦0.1, but substantially below the crystallization temperature of Ba[Al₂Si₂O₈].
 2. The method of claim 1, whereby said mixture in step a) comprises at least the following: 10-20 mol % SiO₂, 0-10 mol % Al₂O₃, 30-45 mol % BaO, 30-40 mol % TiO₂.
 3. The method of claim 1, whereby said mixture in step a) further comprises at least one oxide selected from the group consisting of Sb₂O₃, As₂O₃ and Bi₂O₃.
 4. The method of claim 3, whereby said mixture in step a) comprises 0.01 to 3 mol %, preferably 0.1 to 1 mol %, and particularly preferably 0.1 to 0.5 mol % of said at least one oxide selected from the group consisting of Sb₂O₃, As₂O₃ and Bi₂O₃.
 5. The method of claim 1, whereby said mixture in step a) further comprises at least one oxide of an element selected from the group consisting of Sr, Cr, Ce, Pb, La, Sm, Zr, Hf, Nb, V, Y, Sc and Ta.
 6. The method of claim 1, whereby said mixture in step a) further comprises at least one oxide selected from the group consisting of P₂O₅ and B₂O₃.
 7. The method of claim 1, whereby said ceramicization in step d) takes place using an IR radiator.
 8. The method of claim 7, whereby said ceramicization in step d) takes place under PID control with the aid of a pyrometer.
 9. The method of claim 1, whereby said glass phase, during said ceramicization in step d), is held for 1 minute to 1 hour after heating at a temperature in the region of the crystallization temperature of Ba_(x)Z¹ _(1-x)Ti_(y)Z² _(1-y)O₃.
 10. A glass-ceramic comprising, as main crystalline phase, a perovskite phase of the following formula: Ba_(1-x)Z¹ _(x)Ti_(1-y)Z² _(y)O₃, in which Z¹ is an element selected from the group consisting of Sr, Ca, Ce, Pb, La and Sm, in which Z² is an element selected from the group consisting of Zr, Hf, Nb, V, Y, Sc and Ta, and in which x and y are each independently of one another 0≦x,y≦0.5, preferably 0≦x,y≦0.1, whereby the size of crystallites is in the range of 10 nm to 50 μm, preferably of 100 nm to 1 μm.
 11. The glass-ceramic of claim 10, wherein a volumetric content η of the perovskite phase is 0.3≦η≦0.95.
 12. The glass-ceramic of claim 10, further comprising an oxide selected from the group consisting of Sb₂O₃, As₂O₃ and Bi₂O₃.
 13. The glass-ceramic of claim 12, comprising 0.01 to 3 mol %, preferably 0.1 to 1 mol %, and particularly preferably 0.1 to 0.5 mol % of said at least one oxide selected from the group consisting of Sb₂O₃, As₂O₃ and Bi₂O₃.
 14. The glass-ceramic of claim 10, further comprising at least one oxide selected from the group consisting of P₂O₅ and B₂O₃.
 15. The glass-ceramic of claim 10, having a dielectric constant of ∈′>4000, preferably of ∈′>6000 and particularly preferably of ∈′>8000.
 16. The glass-ceramic of claim 10, having a dielectric loss angle at 10 kHz of tan δ<5·10⁻², preferably of tan δ<2·10⁻².
 17. The glass-ceramic of claim 10, having a dielectric strength given a thickness of 100 μm of >20 kV/mm, preferably of >100 kV/mm.
 18. A glass-ceramic produced according to claim
 1. 19. An electronic component comprising a dielectric, whereby the dielectric comprises a glass-ceramic of claim
 10. 20. The electronic component of claim 19, selected from the group consisting of capacitors, frequency filters and antennas.
 21. The electronic component of claim 20, whereby said capacitor is a high-performance capacitor.
 22. An electronic component comprising a dielectric, whereby the dielectric contains a glass-ceramic of claim
 18. 23. The electronic component of claim 22, selected from the group consisting of capacitors, frequency filters and antennas.
 24. The electronic component of claim 23, whereby said capacitor is a high-performance capacitor. 